Method of making a retroreflective article and a retroreflective article having an aluminum reflector

ABSTRACT

A process for making a retroreflective article that includes the steps of providing a device (tool or a mold) having a first structured surface; applying a reflective layer on the first structured surface resulting in a first adhesion value between the reflective layer and the first structured surface, the reflective layer having an exposed surface; applying a molding polymer to the exposed surface of the reflective layer resulting in a second adhesion value between the reflective layer and the molding polymer. The second adhesion value is higher than the first adhesion value. The device is separated from the molding polymer to yield a retroreflective article that has a second structured surface that is the reverse image of the first structured surface. The separation causes a transfer of the reflective layer from the first structured surface to the retroreflective article. The method allows the reflective layer to be formed during the separation step, rather than being formed independent of creating the second structured surface. The method can yield a article that has a second structured surface coated with an aluminum reflective material having aluminum microstructures that are predominantly amorphous on a first side (the side near the second structured surface) and predominantly crystalline on a second side, which is opposite the first side.

[0001] The present invention pertains to a method of making aretroreflective article, which includes the steps of applying a moldingpolymer to a reflective coated microstructured tool and causing atransfer of the reflective layer from the tool to the article. Theinvention also pertains to retroreflective articles that have astructured surface and an aluminum reflective layer disposed on thatsurface, where the reflective layer adjacent to the structured surfacehas atoms arranged in a predominantly amorphous arrangement.

BACKGROUND

[0002] Retroreflective articles have the ability to return substantialquantities of incident light, which otherwise would be reflectedelsewhere, back towards the light source. This unique ability has led towidespread use of retroreflective articles in a variety of applicationsrelating to traffic and personal safety. For example, in the personalsafety area, retroreflective articles have been used on clothing,primarily to enhance a pedestrian's visibility to motor vehicleoperators after dusk or under other low visibility conditions. They alsohave been attached to book-bags and backpacks for the same purpose.Retroreflective articles can be made from cube-corner structures, suchas cube-corner elements and cube-corner shaped cavities.

[0003] Cube-corner elements are structures that resemble the corner of aroom—that is, they contain three generally perpendicular faces that meetat a point or an apex. Cube-corner cavities, on the other hand, arestructures that are defined by a recessed area bounded by threegenerally perpendicular faces that meet at a point in a valley. Ingeneral, the cube-corner formation process, whether forming cube-cornerelements or cube-corner shaped cavities, is referred to as“replication.” Numerous methods exist for making cube-cornerretroreflective articles. For example, U.S. Pat. No. 5,450,235 to Smithet al. discloses an extrusion method, where a stream of polymer melt isextruded into a microstructured mold containing a multitude ofcube-corner shaped cavities. The resulting product is a microstructuredarticle that has a plurality of cube-corner elements arranged in anarray. U.S. Pat. No. 5,691,846 to Benson, Jr. et al. discloses anothermethod, where a curable resin solution is applied to a mold having amultitude of cube-corner shaped cavities. An overlay film is allowed tocontact the resin. The resin solution is cured using actinic radiationto form a composite sheeting that has an array of cube-corner elementsbonded to the overlay film.

[0004] Cube-corner shaped cavities have been made by various methods.Such methods, however, typically have separated the process of making aretroreflective article from the process of process of metalizing thearticle—that is, the process of applying a reflective layer onto thearticle.

[0005] For example, U.S. Pat. No. 3,712,706 to Stamm discloses areflective surface having an array of cube-corner shaped cavities. Stammdiscloses a method where a cube-corner structure is made by inscribingthree parallel equidistant intersecting grooves on a flat surface of ametal plate. This inscribing process forms a continuous pattern of sharppointed, solid triagonal pyramids with 90° internal dihedral angles. Adihedral angle is the angle formed by two intersecting planes. Stammexplains that the pyramid pattern is a negative form of the desiredcube-corner shaped cavity pattern. The negative form (i.e., the pyramidpattern) may be used as a die for impressing the desired array ofcube-corner cavities in a flat plastic surface or in metal foil. Thecavity array can be mirror coated on all faces with, for example,evaporated gold, aluminum, or chromium. The cube-corner cavities arefilled with an optically transparent solid medium to complete the makingof the retroreflector.

[0006] U.S. Pat. No. 4,127,693 to Lemelson discloses another method ofmaking cube-corner shaped cavities. In one embodiment, a reflectordevice comprises a base member that is capable of being molded orembossed with a plurality of cavities, each cavity being shaped todefine a cube-corner reflector. The cavities have walls that arecomposed of three or more triangular flat surfaces. In a separate step,a thin film of metal may be deposited against the cavity surfaces. Aprotective transparent sheet can be placed over the cavities.

SUMMARY

[0007] The present invention provides a new method of making aretroreflective article, which method can allow the article to be formedand made reflective contemporaneously. In brief summary, the inventivemethod comprises: (a) providing a device that has a first structuredsurface; (b) applying a reflective layer on the first structured surfacesuch that a first adhesion value is established between the reflectivelayer and the first structured surface, the reflective layer having anexposed surface; (c) applying a molding polymer to the exposed surfaceof the reflective layer such that a second adhesion value is establishedbetween the reflective layer and the molding polymer, the secondadhesion value being higher than the first adhesion value; and (d)separating the device from the molding polymer to yield theretroreflective article having a second structured surface, theseparation causing a transfer of the reflective layer from the firststructured surface to the retroreflective article. The device can be atool or a mold. The inventive method differs from known methods in thatit can combine the process of forming the second structured surface andapplying a reflective layer in essentially a single step. When thereflective layer used in the method includes aluminum, applicantsdiscovered that a new article was produced that had aluminummicrostructures that are predominantly amorphous on a first side (theside near or next to the second structured surface) and predominantlycrystalline on a second side (the side furthest away from the secondstructured surface).

[0008] An advantage of the method of the present invention is that itcan eliminate the need to form the reflective layer directly on theinventive article. Because of the high temperature and high vacuumprocessing conditions typically present in many vapor depositionprocesses, residual solvents or monomers contained in a polymeric toolor mold can sometimes outgas and can cause blisters and defects in thereflective coating. When reflective layers have been deposited directlyonto a polymeric tool or mold, investigators have had to take care inselecting ones that are capable of withstanding the vapor depositionprocess conditions. The differences between a tool and a mold aredefined in detail below. The method of the present invention, however,provides the advantage in that the reflective layer is not directlyvapor deposited to the second structured surface of the inventivearticle and therefore may not significantly impose upon the types ofmaterial that may be selected to make the inventive retroreflectivearticle.

[0009] The new retroreflective article of the invention comprises: (a) astructured surface that is configured for allowing the article toretroreflect incident light; and (b) an aluminum reflective layerdisposed on the structured surface, the aluminum layer having first andsecond sides, the first side disposed towards the structured surface andlies opposite the second surface, wherein the first side has an aluminummicrostructure in a predominantly amorphous arrangement.

[0010] Retroreflective articles of the invention, which possess analuminum-containing reflector, differ from known retroreflectivearticles in regard to the arrangement of the aluminum atoms. Unlike thearticles described in U.S. Pat. Nos. 3,712,706 and 4,127,693, thepresent inventive article includes an aluminum reflective layer wherethe aluminum atoms disposed towards the structured surface have agenerally amorphous arrangement and the metal atoms away from thestructured surface have a generally crystalline arrangement.

BRIEF DESCRIPTION OF THE DRAWINGS

[0011] The invention is further explained with reference to thedrawings, wherein:

[0012]FIG. 1 is a top view of a known array 50 of cube-corner elements2;

[0013]FIG. 2 is a cross-sectional view of a retroreflective article 10in accordance with the invention;

[0014]FIG. 3 is a cross-sectional micrograph (magnified about 67,950times, such that 0.675 centimeters on the micrograph equals 100 nm inactual length) of an aluminum reflective layer 84 deposited on anacrylate substrate 80 (the micrograph was obtained from a transmissionelectron microscope); and

[0015]FIGS. 4 and 5 are cross-sectional views depicting the method ofthe present invention.

[0016] These figures are idealized, are not to scale, and are intendedto be merely illustrative and non-limiting.

DEFINITIONS

[0017] As used in this document in reference to the invention:

[0018] a reflective layer having a “predominantly amorphous arrangement”means that the atoms, molecules, or ions in the layer lack organization,such as periodicity or repetitive arrangement;

[0019] a reflective layer having a “predominantly crystallinearrangement” means that the atoms, molecules, or ions bonded together inthree-dimensions in the layer do exhibit a repetitive or periodic,orderly arrangement;

[0020] “cube-corner shaped cavity” means a recessed area bounded atleast in part by at least three optical faces and may includenon-optical faces;

[0021] “cube-corner element” means a body, such as a pyramid, projectingfrom a surface, where the body is defined at least in part by at leastthree optical faces and may include non-optical faces;

[0022] “faces” of a cube-corner element are planes that intersect oneanother;

[0023] “mold” is a device that has a plurality of cavities, such ascube-corner shaped cavities, that define a first structured surface,which can be used with a molding polymer to create an article having asecond structured surface defined by a plurality of elements, such ascube-corner elements;

[0024] “molding polymer” is a natural or synthetic compound, usually ofhigh molecular weight (greater than about 1000 gram/mole), that containsrepeated linked units and that can have adhesive properties (such astackiness) at room temperature;

[0025] “non-optical faces” in a cube-corner element or cube-cornershaped cavity are faces that are incapable of cooperating with otherfaces to retroreflect significant amounts of incident light because thenon-optical faces are substantially non-orthogonal to other faces;

[0026] “optical faces” in a cube-corner element or cube-corner shapedcavity are faces that are substantially mutually perpendicular—that is,the faces form an internal dihedral angle of about 90°, to cooperate toretroreflect incident light;

[0027] “softening temperature” means a temperature as defined by ASTM E28-97;

[0028] “structured surface” means a surface that has a plurality offeatures which is defined by local minima and maxima, the separationdistance between neighboring local minima and maxima being in the rangeof about 0.01 millimeter to 1 millimeter (about 0.0004 to 0.040 inch)such as, for example, cube-corner elements, cube-corner shaped cavities,or combinations thereof; and

[0029] “tool” is a device that has a plurality of elements, such ascube-corner elements, that define a first structured surface, which canbe used with a molding polymer to create an article having a secondstructured surface defined by a plurality of cavities, such ascube-corner cavities.

DETAILED DESCRIPTION OF THE ILLUSTRATIVE EMBODIMENTS

[0030]FIG. 1 shows a topview of a known array 50 that containscube-corner elements 2 projecting from a surface. Each element 2 is inthe shape of a tetrahedral prism that has three exposed optical faces 8and an apex 4. The optical faces of the cube-corner elements define afirst structured surface. Cube-corner elements 2 in known arrays aretypically defined by three sets of parallel v-shaped grooves 5, 6, and7. Adjacent optical faces 8 on adjacent cube-corner elements 2 in eachgroove form an external dihedral angle, which is the angle formed by twointersecting planes. The array 50 can be used as a cube-corner tool formaking an article that bears cube-corner shaped cavities. As shown, eachcube-corner element in the ordered array sits adjacent to one another.The dihedral angle can vary in some embodiments of known cube-cornerarrays as disclosed in U.S. Pat. No. 5,770,124 to Marecki et al.

[0031]FIG. 2 shows an illustrative embodiment of the inventive article10 having a molding polymer 18 and a structured surface 16 defining, inthis case, a plurality of cube-corner shaped cavities 12. Disposed onthe structured surface 16 is a reflective layer 14. If desired, a lighttransmissible protective layer 15 can be used to protect the reflectivelayer 14. As shown, the layer 15 follows the topography of thestructured surface 16. The protective layer 15 can fill a portion of thecavity or fill the entire cavity 12. Other layers may be disposedbetween the molding polymer 18 and the reflective layer 14 such as tielayers. An optional carrier web 20 serves as a support member for themolding polymer 18. Suitable examples of carrier webs include fabricsand polymer films. In use, retroreflection occurs when an incident lightray 22 enters the cavities, strikes the reflective layer 14 on thestructured surface 16, and is returned towards the light source.

[0032] The structured surface is configured to retroreflect incidentlight. The structured surface can be found on the tool (30 in FIGS. 4and 5) and on the inventive article (10 in FIG. 2). When used todescribe the tool or the mold, the term “first structured surface” isusually used. When used to describe the inventive article, the term“second structured surface” is usually used.

[0033] In one inventive embodiment, the structured surface is defined bya plurality of cube-corner shaped cavities, which are formed from aplurality of cube-corner elements present on the tool. A mold, on theother hand, is made of a plurality of cube-corner cavities, in whichcase, the resulting inventive article contains a plurality ofcube-corner elements. Illustrative examples of structured surfaces, oneither a tool or a mold, that are useful for the practice of theinvention are discussed below.

[0034] U.S. Pat. No. 3,712,706 to Stamm discloses a useful cube-cornerelement based on a hexagonal close-packed array of contiguouscube-corner elements, each element having an equilateral base triangledefined by three base edges lying in a common plane and three opticalfaces intersecting at a point. Each element has an optical axis thatextends through the apex and trisects the element's internal space. Theoptical axis is perpendicular to the base triangle.

[0035] U.S. Pat. No. 4,588,258 to Hoopman provides another usefulcube-corner element based on an equilateral base triangle with amodification in that the optical axis is tilted towards one of the basetriangle's base edge. In use, at least one matched pair of cube-cornerelements produces retroreflection. A matched pair of elements occurswhen the elements are rotated 180° with respect to one another.

[0036] Another useful cube-corner design is disclosed in U.S. Pat. No.4,895,428 to Nelson et al. The cube-corner element has a rectangularbase, two tetragonal faces nearly perpendicular to each other and havinga line of intersection. The element contains a triangular face thatintersects nearly perpendicular to the tetragonal faces forming anapproximate cube-corner. The element further contains another triangularface intersecting not perpendicular to the tetragonal faces forming anon-orthogonal face. The non-orthogonal triangular face is not activeoptically. Thus, the cube-corner element has two parallel grooves andappears as a pup-tent type pyramid.

[0037] The foregoing discussion on specific cube-corner element designsmerely illustrates some, but not all, of the types of cube-cornerelements, which are suitable for practicing the present invention. Thereverse image of the cube-corner elements would be the cube-cornershaped cavities. Other designs also capable of retroreflecting somesignificant portion of the incident light are contemplated for use inconnection with the present invention.

[0038] The inventive article has a second structured surface that can beformed when a molding polymer is processed so as to take on the shape of(that is, replicate) the first structured surface of the tool, which hasbeen previously coated with a reflective layer. The molding polymerenables the reflective layer coated on the tool to adhere preferentiallyto the second structured surface. That is, the adhesion between themolding polymer and the reflective layer is higher than the adhesionbetween the first structured surface and the reflective layer. The firststructured surface can be made from a wide variety of materials, rangingfrom metals to polymers. Articles that discuss the adhesion ofreflective metals, which may be suitable for use in reflective layers,for example, aluminum, silver, tin, or gold, on various polymericsubstrates are available in the art.

[0039] For example, adhesion, in terms of peel strength, of an aluminumlayer of about 1000 nanometers thick deposited on a polyetherimidesubstrate has been studied. See, Gregory M. Porta, et al., VacuumMetallization of Polyetherimide: Interfacial Chemistry and Adhesion,Volume 32, No. 15, Polymer Engineering and Science (Mid-August 1992),page 1021-27. The article further describes methods that can increasethe adhesion of aluminum to the substrate, such as, for example, bysurface cleansing before deposition.

[0040] The adhesion of aluminum on various polymer substrates, such asbiaxially oriented polypropylene (BOPP), both untreated and treated withlow pressure O₂ plasma, polyethylene terephthalate (PET), and polyvinylchloride (PVC) have also been studied. See C. H. Bicher, et al.,Adhesion mechanism of aluminum, aluminum oxide, and silicon oxide onbiaxially oriented polypropylene (BOPP), poly(ethyleneterephthalate)(PET), andpoly(vinyl chloride) (PVC), Volume 11, No. 2, Journal ofAdhesion Science & Technology (1997), page 233-246. The aluminum isevaporated in a vacuum web coater using an electron beam from awater-cooled crucible. The aluminum layer was about 60 nanometer (nm)thick.

[0041] The adhesion of gold and aluminum, among other metals, onMelinex® 505, Melinex® 442 (both of which are polyester based film), andpolystryene have been studied. See M. E. Kordesch and R. W. Hoffman,Strongly Adhesive Gold Electrodes on Melinex®, Volume 107, Thin SolidFilms, (1983), page 365-371. The article reports that both types ofMelinex® are commercially available from ICI Americas, Inc. The goldfilms are vacuum evaporated to a thickness of about 10 to 50 nm.

[0042] Preferably, the molding polymer replicates the tool's structuredsurface as precisely as possible so as to capture substantially itsentire shape. For this to occur, the molding polymer preferably fillsthe valleys or recessed area on the tool's structured surface. Thereplication process desirably produces a second structured surface thathas substantially flat faces to aid in retroreflective efficiency. Themolding polymer is preferably sufficiently stable so that it will notdistort, sag, or change shape over time. For retroreflective articlesthat are used on clothing, the second structured surface preferablymaintains its shape even after repeated exposure to laundering cycles inwashing machines. The thickness of the molding polymer is typicallysufficient so as to replicate the tool's structured surface entirely.Preferably, there is sufficient molding polymer to join the secondstructured surface of the inventive article in a continuous array. Theamount of molding polymer used, however, should not be so thick as toreduce the inventive article's flexibility or so as to be costprohibitive.

[0043] The molding polymer may be a thermoplastic or thermoset polymer.Suitable examples of thermoplastic polymers include ethylene copolymerscontaining carboxyl groups or esters of carboxylic acids, polyethyleneacrylate, polyesters, polyurethanes, polyamides, polyester amides, andcrystalline rubber based polymers. The softening temperature of thethermoplastic polymer preferably is less than 450° F., and morepreferably less than 350° F., as determined by ASTM E28-97 entitled“Softening Point of Resins by Ring-and-Ball Apparatus.” A suitableexample of a thermoset polymer is ethylene acrylic acid (EAA) that hasbeen cross-linked using actinic radiation, such as electron beamradiation.

[0044] Another suitable molding polymer is a hot melt adhesive. Theadhesive may be a thermoplastic or thermoset polymer. Generally, a hotmelt adhesive uses components, including solventless polymers andadditives, such as tackifying resins and plasticizers. The componentsare processed so as to flow or creep under stress. Typically, they areprocessed using extrusion. U.S. Pat. No. 5,257,491 to Rouyer discloses amethod of packaging an adhesive composition, especially a thermoplasticor thermoset hot melt adhesive composition. When Rouyer's hot meltadhesive is used in the present invention, it may be extruded directlyonto the first structured surface, which has been previously coated witha reflective layer. Alternatively, the hot melt adhesive can be extrudedonto a carrier, such as a fabric or a polymeric film, and laminated tothe first structured surface, which has been previously coated with areflective layer. Depending on the chemistry of the hot melt adhesive,it can be cured by ultraviolet light or electron beam radiation.

[0045] U.S. Pat. Nos. 5,539,033 and 5,550,175, both to Bredahl et al.,disclose solventless hot melt processes to prepare non-thermosettablepressure sensitive adhesives (PSA) useful in the present invention. Bothprocesses use a continuous, compounding device that has a sequence ofalternating conveying and processing zones. The processes allow forprocessing of non-thermoplastic hydrocarbon elastomers and tackifiers,without using organic solvents or low molecular weight plasticizingagents, both of which reduce the viscosity of the composition to renderit processable. U.S. Pat. No. 5,539,033 discloses a wide variety ofnon-thermoplastic hydrocarbon elastomers and tackifiers. Examples of theelastomers include natural rubber, butyl rubber, synthetic polyisoprene,ethylene-propylene rubber, ethylenepropylene-diene monomer rubber(EPDM), polybutadine, poly-(alpha-olefin), and styrene-butadiene randomcopolymer rubber. Examples of useful tackifiers include rosin and rosinderivatives, hydrocarbon tackifier resins, aromatic hydrocarbon resins,and terpene resins, all of which are used from 10 to 200 parts by weightper 100 parts by weight of the elastomer.

[0046] U.S. Pat. No. 5,141,989 to Jung et al. discloses yet anothermolding polymer useful in the present invention. Jung teaches ascreen-printable acrylate PSA composition essentially comprising (1) adissolved polymeric solid comprising at least one acrylate copolymer,and (2) a polar low molecular weight solvent in which the acrylatecopolymer is dissolved. Jung discloses that at the screen printingstage, the acrylate copolymer has an inherent viscosity of less than 1.0deciliter/gram, and that a particularly useful inherent viscosity is oneof about 0.45 dl/g. At the lower viscosity, the PSA composition flowsout quickly and smoothly to form a planar and even coating. Jungindicates that the PSA exhibits high stability against water andmoisture so that it may be used for outdoor applications.

[0047] The reflective layer is typically opaque and preferablyspecularly reflective, although other reflective layer types can beused. The reflective layer is preferably metallic. Suitable materialsfor use as reflective layers include aluminum, gold, silver, tin andcombinations thereof. Aluminum and silver are used commonly to provide aspecular reflector. In some cases, gold is a useful specular reflectorbecause of its inert properties, making it resistant to corrosion, andbecause of its color. Dielectrics may also be used as a reflective layer(see U.S. Pat. No. 4,763,985 to Bingham).

[0048] The reflective layer is typically about 100 to 1500 nanometers(nm) thick, preferably about 500 to 1200 nm thick. By using the vapordeposition processes, the reflective layer is deposited initially on thefirst structured surface. For a description of the different vapordeposition processes, see Thin Films, Volume 23, Kirk-OthmerEncyclopedia of Chemical Technology, 4^(th) edition, (1997), pages1040-1050. In addition, the reflective layer can be formed by spraycoating. The reflective layer is desirably uniformly deposited and liessubstantially flat on the first structured surface. If the reflectivelayer starts out uniform and flat on the first structured surface, thenthere is a better chance that it will remain uniform and flat after itstransfer to the molding polymer.

[0049]FIG. 3 is a transmission electron microscope (TEM) micrographdepicting the microstructures of the aluminum reflective layer 84deposited onto a cube-corner tool 80. The tool has a first structuredsurface 82 made from an acrylate polymer. For TEM analysis, thealuminum-coated tool is encased in an embedding resin 90 and iscross-sectioned. The aluminum layer is deposited onto the firststructured surface as described below in the Example section.

[0050] As can be seen, the aluminum layer 84 has two types ofmicrostructure. Near the surface 82, the aluminum atoms are in apredominantly crystalline arrangement as shown by the grain likestructures, some of which appear as dark regions. As more aluminum atomsare deposited (to form the reflective layer), they change from acrystalline arrangement to an amorphous arrangement until at thereflective layer's exposed surface 86 (which has been covered byembedding resin 90 in FIG. 3), the aluminum atoms are predominantlyamorphous in arrangement. In the amorphous region, there is an absenceof grain structures and the surface 86 appears to have a rough surfacetexture. When the molding polymer is applied to the reflective layer 84,it first contacts the amorphous side of the reflective layer and thepredominantly crystalline side becomes exposed to the atmosphere, unlessit is covered by a protective coating (not shown).

[0051] Depending on the reflective material used, a protective layer canbe used to suppress the effects corrosion may have on the reflectivelayer. As shown in FIG. 2, the reflective layer 14 is coated with aprotective layer 15. In general, corrosion is the destructive attack ofa metal by chemical or electrochemical reactions with its enviromnent.

[0052] The protective layer functions mainly to protect the reflectivelayer from adverse effects of the environment. Such adverse effects mayreduce the reflective layer's ability to redirect incident light. Suchadverse effects include, for example, corrosion of the reflective layer,dirt accumulation on the reflective layer, or attack of the reflectivelayer causing it to chip, flake, and crack.

[0053] When an aluminum reflective layer is exposed to air, a layer ofaluminum oxide, Al₂O₃, typically forms. The oxide bonds strongly to thealuminum layer and protects it from further oxidation. A thin layer ofaluminum oxide is light transmissible, allowing a portion of theincident light to strike the underlying aluminum reflective layer. Theoxide layer is estimated to be about 2 to 10 nanometers thick. Oneskilled in the art can reasonably expect that the inventive articlehaving an aluminum reflector layer coated in the cube-corner shapedcavities will be stable in air. There is concern that because thealuminum reflector layer is typically thin, that is, on the order ofabout 500-1500 nanometers, that with time the aluminum oxide layer canconsume the aluminum. If so, the aluminum could be depleted resulting inan article with substantially no reflector. In such a case and in othersituations, a light transmissible protective layer can be used toprotect the aluminum reflective layer.

[0054] The aluminum reflective layer also may need protection if it isexposed to water. Although aluminum is generally stable in distilledwater, it tends to pit in waters containing chloride ions, Cl⁻,particularly at crevices, such as in the valleys of a structuredsurface. Aluminum corrodes more rapidly in both acidic and basicsolutions compared to distilled water. Thus, if the inventive articlehas an exposed aluminum reflective layer and the article is exposed tobasic laundry detergents at elevated temperatures, supplied for exampleby warm water, the aluminum reflective layer may likely corrode.

[0055] The different mechanisms of providing a protective layer includeusing a protective polymeric film to cover the cube-corner cavities,using a corrosion resistant coating on the cube-corner elements orcavities, or filling the cavities with a polymer. There are severalknown methods to protect aluminum reflective layers. For example, plasmapolymerization has been use to form organosilicone thin films forprotecting aluminum reflector films for the automotive headlightindustry. The films are also used as clear protective top coats onoptical reflective films. See Thin Films, Vol. 23, Kirk-OthmerEncyclopedia of Chemical Technology, 4^(th) Ed. (1997), starting at page1066. In general, plasma polymerization is a process of forming thinpolymer films using plasma, a partially ionized gas. In one method,plasma polymerization is carried out using an electric glow discharge ina vacuum. Plasma polymerization forms thin polymeric films that, in mostcases, are highly branched and highly crosslinked from low molecularweight materials that are soluble in solvents. See H. Yasuda, PlasmaPolymerization, Academic Press, New York, page 1-5 (1985).

[0056] Another method of protecting the reflective layer involvesforming a layer of light transmissible acrylic over the aluminumreflective layer. For example, a solution of acrylic resin can besprayed over the second structured surface of the inventive article. TheHenkel Corp. located in Ambler, Pa., USA has a commercially availableacrylate coating that is clear, i.e., light transmissible. Theformulation is described in Henkel's January 1997 Data Sheet entitled“Formulation Guide E—Ultraviolet Metal Coatings and Inks.” If desired,the protective layer can include a light transmissible colorant toimpart a desired color to the inventive article.

[0057] When a silver reflective layer is exposed to air, it issusceptible to corrosion, such as tarnishing, caused by the formation ofsulfur compounds such as silver sulfides, Ag₂S. These compounds have ayellowish to tan appearance affecting adversely the reflectivityperformance of the silver reflective layer. Silver can also be oxidizedto form layers of silver oxides. A layer of silver oxide usually doesnot bond strongly to the underlying silver reflective layer. The silveroxide tends to crack and fall off exposing fresh silver surface forfurther oxidation. As the oxidation process progresses, the silverreflective layer can be consumed.

[0058] Silver reflective layers have some advantages over aluminum. Forexample, silver is more reflective than aluminum, reflectingapproximately at 98% of the incident light compared to 91% for aluminum.Silver also has a whiter appearance, which is usually a desirablefeature because true colors can be achieved. In general, an articleusing an aluminum reflective layer has a gray appearance due to thecolor of the aluminum. Some investigators wanting the advantages of asilver reflective layer have found ways to protect the silver reflectivelayer.

[0059] U.S. Pat. No. 4,645,714 to Roche et al. discloses usefulmercaptans to protect silver mirrors. Mercaptans belong to a group oforganosulfur compounds and have the general structure, RSH, where R isany radical, such as, e.g., a benzene ring or an alkane. Roche teachesan embodiment comprising (1) a co-extruded biaxially oriented polyesterfilm, (2) an opaque silver reflecting layer vapor deposited over thepolyester film, (3) a coated layer of stable mercaptan, and (4) aprotective polymer layer containing ultraviolet light absorbersoverlying the mercaptan layer. Roche defined “stable mercaptan” to meanthose in which the alpha carbon atom (the one bearing the sulfur) isotherwise attached only to carbon and hydrogen atoms and should have oneor more polarizable groups at or near the end of the molecule to enhancecompatibility with the polymer used in his protective layer. Themercaptans listed protect silver from corrosion and also act as anadhesion promoter, coupling agent, or primer for Roche's protectivelayer. Mercaptans generally have a slight yellowish hue. When coated ina monolayer, however, the mercaptan is substantially light transmissibleand thus does not interfere with the silver layer's ability toretroreflect incident light.

[0060] Illustrative mercaptans suitable for the invention, as listed inU.S. Pat. No. 4,645,714, include mercaptoacetic acid,3-mercaptopropionic acid, 11-mercaptoundecylic acid, thiophenol,diphenyl disulfide, N-(2-hydroxyethyl)mercaptoacetamide,2,2′-dimercaptodiethyl ether, 2,2′-dimercapto diethyl thioether,1,2-ethanedithiol, 3-mercaptopropyl trimethoxysilane, glycolbis(3-mercaptopropionate), trimethylolpropranetris(3-mercaptopropionate), and glycol dimercaptoacetate. About 0.5 to2.5 weight percent of the mercaptan is dispersed in an acrylate ormethacrylate interpolymer, which is described below. The weight percentis based on the total weight of the acrylates. Added to the mercaptanand the acrylate interpolymer is a carrier, typically a solvent. Thesolution can be spray coated on to inventive article's structuredsurface and then heated to evaporate the solvent.

[0061] The interpolymer Roche uses comprises or consists essentially of(1) about 50-70% monomers selected from the class consisting of methylmethacrylate and ethyl methacrylate and (2) correspondingly about 30-50%monomers selected from the class consisting of butyl acrylate, butylmethacrylate, and 2-ethylhexyl acrylate, the interpolymer dispersed in a45% toluene solution.

[0062] Silver is known to be transmissible in the ultraviolet (UV) lightrange of about 300 to 400 nanometers wavelength. Such light can passthrough the silver film and affect the underlying molding polymer.Consequently, a light transmissible layer has been used which containsadditives to absorb UV light in the 300 to 400 nanometers range. UVabsorbers such as benzotriaole, in about 5 weight percent of theacrylate, can be added to the interpolymer described above. Typically,the acrylic layer containing the UV absorbers is coated on top of thelayer containing the mercaptan. U.S. Pat. No. 4,645,714 disclosesseveral examples of benzotriazole commercially available from theCiba-Geigy Corporation, Hawthorne, N.Y., USA under trade names TINUVIN™234 and TINUVIN™ 328.

[0063] When the reflective layer is gold, a suitable protective layer isa light transmissible polyurethane. Regardless of the type of reflectivelayer (i.e., whether dielectric or metallic, and in the latter case,whether aluminum, gold, or silver), a light transmissible polymeric filmcan be used to cover the cube-corner shaped cavities. The film caninclude additives such as colorants and ultraviolet light stabilizers,as long as the additives preferably allow a portion of the incidentlight to transmit into and be reflected by the inventive article. Forcertain applications, the polymeric films are preferably flexible innature and may include polyvinyl chloride and polyurethane having anelastic modulus of less than about 7×10⁸ pascals. If used, the polymericfilm is preferably about 0.0005 to 0.015 inch (0.013 to 0.38 millimeter)in thickness.

[0064] Yet another method of protecting the reflective layer is to fillthe entire cube-corner cavity with a filling polymer, which is a lighttransmissible polymer. Any light transmissible polymer capable of beingextruded or coated into the cavities of the inventive article can beused.

[0065] Method of Making

[0066]FIG. 4 shows an illustrative method of the invention where a tool30 has a first structured surface 36 formed from a plurality ofcube-corner elements 38 that project outwardly from a major surface 34of a support layer 32. The tool 30 may be flexible or rigid. Theelements 38 and the support layer 32 can be made from the same or fromdissimilar materials. In the case of a flexible tool, a liner (notshown) may be used next to the support layer 32 to impart stability tothe tool during processing. Typically, the flexible tool has dissimilarmaterials for the elements 38 and the layer 32. For example, theelements 38 can be one type of polymer, typically a rigid polymer, whilethe layer 32 can be of another type of polymer, typically a moreflexible polymer than the elements 38. In the case of a rigid tool, forexample, a metal tool, the layer 32 and elements 38 are typically madeof a similar material. FIG. 1 shows a top view of an array 10 that maybe useful as a tool for the practice of this invention.

[0067] A reflective layer 14 is coated on the structured surface 36.Reflective layer 14 has an exposed surface 37. The reflective layer canbe made by vapor depositing aluminum, gold, silver, tin, et cetera usingvacuum deposition or vacuum evaporation. The layer 14 is preferably ofuniform thickness at different locations on the structured surface 36.When vapor deposition is used, the elements 38 preferably are made froma material that can withstand exposure to the high temperature, highvacuum conditions that are used in a typical vacuum deposition process.Temperature stable materials may include, for example, polycarbonate andacrylate.

[0068] A composite layer 40 comprises a molding polymer 18 optionallypre-attached to a carrier web 20, such as a fabric. The molding polymercan have a surface 46 that is initially substantially flat. Attachmentto the carrier can be accomplished by conventional laminatingtechniques. One such technique uses two rollers positioned sufficientlyclose to one another so as to create a nip between them. The carrier web20 is allowed to contact one roller. The molding polymer, typically on aliner, is allowed to contact a second roller, usually with the liner indirect contact with the second roller. Using pressure and heat, ifnecessary, the molding polymer 18 and carrier web 20 are intimatelyjuxtaposed against each other. The molding polymer 18 can also beapplied directly to the carrier web 20 by using known extrusion orcoating techniques. The composite 40 is then applied to the tool 30 suchthat the molding polymer's exposed surface 46 contacts the reflectivelayer's exposed surface 37. Various methods of combining the composite40 and the tool 30 are discussed in detail below.

[0069] The molding polymer 18 functions to replicate, that is, take onthe shape of the structured surface 36, and to transfer the reflectivelayer from the tool to the molding polymer, which eventually becomes apart of the retroreflective article. Preferably, the replication ofstructured surface 36 is as precise as possible capturing essentiallyall the features of the structured surface 36. The replication step canbe accomplished by applying the composite 40 to the tool 30 usingseveral different methods.

[0070] In one method, the composite 40 is laminated to the tool 30. Thelamination step typically uses heat and pressure. As shown in FIG. 4,the composite layer 40 is placed so that the molding polymer 18 facesthe tool 30. For batchwise production, the composite and the tool aretypically sandwiched between several skin layers, such as polyesterand/or thick aluminum plates (not shown) and placed in a heated press.Using sufficient heat and pressure, the molding polymer 18 is intimatelyjuxtaposed against the tool 30 to replicate the shape of the structuredsurface 36. Typically, the composite 40 is allowed to cool before it isremoved from the tool 30.

[0071]FIG. 5 shows that after the replication process, the tool 30 isseparated from the article 60. During the separation step, thereflective layer 14 transfers from its initial position (on the firststructured surface 36) to the second structured surface 46 of themolding polymer. Preferably, there is a clean transfer of the reflectivelayer 14 from the tool to the inventive article. A “clean transfer” ofthe reflective layer means that substantially all of it has moved fromthe initial position (on the tool) to the final position (on theretroreflective article). A clean transfer of the reflective layer isdesirable as it insures that the structured surface of the inventivearticle is capable of retroreflecting incident light as efficiently aspossible. In a continuous process, the lamination step integrates thereplication step and the reflective layer transfer step by using acombination of hot cans and pressure rolls to supply the heat andpressure, much like the process described above for laminating themolding polymer 18 to the carrier 20.

[0072] The retroreflective article 60, after being removed from the tool30, has an exposed reflective surface 14. A protective layer (not shown)can be applied to such a surface to minimize corrosion of the metallayer. The protective layer is preferably about 0.1 to 10 micrometerthick. In an alternative method, the protective layer can be applied tothe structured surface 36 before applying the reflective layer 14. Inthis case, the protective layer most likely follows the topography ofthe surface 36. The protective layer is deliberately chosen to havebetter adhesion to the reflective layer than to the structured surface36. During transfer of the reflective layer 14, the protective layertransfers with the reflective layer to the retroreflective articlecausing the protective layer to be exposed to ambient conditions. Anillustrative protective layer is a thin light transmissible layer oftitanium on a tool having a first structured surface made from anacrylate. A useful molding polymer is EAA.

[0073] In another embodiment of the inventive method of making aretroreflective article, the method comprises: (a) providing a devicecomprising a first structured surface; (b) applying a protective layeron the first structured surface such that a first adhesion value isestablished between the protective layer and the first structuredsurface, the protective layer having an exposed surface; (c) applying areflective layer on the exposed surface of the protective layer suchthat a second adhesion value is established between the protective layerand the reflective layer; (d) applying a molding polymer to the exposedsurface of the reflective layer such that a third adhesion value isestablished between the reflective layer and the molding polymer, thesecond and third adhesion values being higher than the first adhesionvalue; and (e) separating the device from the molding polymer to yieldthe retroreflective article having a second structured surface, theseparation causing a transfer of the protective and reflective layersfrom the first structured surface to the retroreflective article.

[0074] If desired, a tie layer (not shown) can be applied to the exposedsurface of the reflective material 14. The tie layer can be selected soas to be compatible with the molding polymer 18 and the reflective layer14. For example, a polyurethane tie layer having good adhesion to analuminum reflective layer could provide increased adhesion to the entirearticle when a polyurethane molding polymer is used.

[0075] Although the inventive methods described thus far use a toolhaving a plurality of cube-corner elements, the inventive method can bepracticed with a mold that has a plurality of cube-corner shapedcavities. Thus, the molding polymer can be in liquid form and coatedonto a mold. Using various coating techniques, the polymer is encouragedto cure by various known methods, such as drying or radiation curing.

[0076] In one coating method, the polymer is coated by screen printing,which allows the polymer to contact selective regions of the mold,typically by pouring or notch bar coating a quantity of the moldingpolymer through a screen mesh having a specific graphic design to createan image or text. The screen mesh-size controls the amount of polymerthat contacts the mold. The amount of molding polymer used should besufficient to cover the mold to replicate the entire first structuredsurface. Preferably, excess molding polymer is used so as to create aregion joining the molding polymer together. Typically a carrier web,such as a fabric, is laminated to the side of the molding polymer not incontact with the mold. In this way, retroreflective graphic images canbe made.

[0077] In another embodiment of the inventive method, the liquid moldingpolymer is coated to a mold as disclosed in U.S. Pat. No. 5,691,846 toBenson Jr., et al. A method of making a retroreflective articlecomprises the steps of: (a) providing a mold having a plurality ofcube-corner cavities defining a first structured surface; (b) applying areflective layer on the first structured surface such that a firstadhesion value is established between the reflective layer and the firststructured surface, the reflective layer having an exposed surface; (c)applying a volume of a molding polymer to the first structured surfacesuch that a second adhesion value is established between the reflectivelayer and molding polymer, the second adhesion value being higher thanthe first adhesion value; (d) contacting a carrier web to the moldingpolymer; (e) minimizing excess molding polymer extending above the firststructured surface; then (f) curing the molding polymer while in contactwith the carrier web, and (g) separating the mold from the cured moldingpolymer to yield the retroreflective article having a second structuredsurface, the separation causing a transfer of the reflective layer fromthe mold to the retroreflective article. As a result of this process,the inventive article contains a second structured surface that bears aplurality of cube-corner elements coated with a reflective layer. Theresin can be cured using actinic radiation, such as, e.g., electronbeam, ultraviolet light (UV), or visible light. When UV or visible lightis used, the carrier web is transparent to the respective light sourceso as to allow a portion of the light through to cure the moldingpolymer.

[0078] Other processing considerations can also to be taken intoaccount. For example, before removing the tool or mold, the moldingpolymer is allowed to cool sufficiently to give structural integrity tothe second structured surface. Typically, the entire composite (that is,the tool or mold, reflective layer, molding polymer, and carrier) isallowed to cool. Removing the tool or mold before the molding polymercools sufficiently can yield cube-corner structures that are formedimprecisely. This lack of precision can reduce retroreflectiveefficiency of the inventive article.

[0079] In another embodiment of the inventive method, the moldingpolymer 18 may be a polymer melt exiting an extruder die. Conventionalextrusion coating processes can be used. The polymer melt contacts thereflective coated tool 30 thereby replicating the first structuredsurface 36. Additional heat and pressure can be used, if needed, duringextrusion to further aid precise replication of the structured surface36. If desired, a carrier 20 can be laminated to exposed surface of themolding polymer, that is, the surface not in contact with the mold. Themolding polymer is removed from the tool or mold so as to allow a cleantransfer of the reflective layer.

EXAMPLES

[0080] The following examples are provided to illustrate differentembodiments and details of the invention. Although the examples servethis purpose, the particular ingredients and amounts used, as well asother conditions and details, are not to be construed in a manner thatwould unduly limit the scope of the invention. Unless specifiedotherwise, all percentages are weight percentages.

[0081] Brightness Measurements

[0082] Measurements of the coefficient of retroreflection (brightnessmeasurements), R_(A), were taken of the samples below using standardphotometric equipment and techniques as generally described in ASTM E808-94. The actual test method used to obtain R_(A) values reported inthe Examples are traceable back to ASTM E 808-94. The observation anglewas set at 0.2 degree, the entrance angle was set at −4 degree, and therotation angle of the sample was set at 0 degree, all of the anglesbeing defined as in the test method.

Example 1

[0083] A reflective sheeting, commercially available from MinnesotaMining and Manufacturing (3M), St. Paul, Minn., USA as 3M™ Scotchlite™High Gloss Reflective Film Unsealed 6160 (referred to as “High Glosstool”), was used as a flexible, cube-corner tool. The tool hadcube-corner elements (prisms) having a depth of about 0.0034 inch (0.086mm). The cube-corner elements are formed as matched pairs. The opticalaxis of each element was canted or tilted about 4.31 degrees away fromthe primary groove, as generally illustrated in U.S. Pat. No. 5,138,488to Szczech.

[0084] On the structured surface where cube-corner elements' faces arepresent, a layer of aluminum about 800 to 850 nanometers thick was vapordeposited. The aluminum reflective layer is deposited using an electronbeam vacuum coater pulling a vacuum at about 6×10⁻⁶ torr and anevaporation rate of about 18 to 24 angstroms per second. The vacuumcoater used was a CHA Industries Mark 50 model (available from CHAIndustries, Freemont, Calif., USA).

[0085] A 0.003 inch thick (0.076 mm) ethylene methacrylic acid (EMAA)molding polymer film (available from DuPont Co., Willimington, Del., USAas Nucrel™ 699 adhesive) was laminated to a polyester blend fabricavailable as Excellerate™ (a 65%-35% polyester-cotton blend availablefrom Spring Industries, Rock Hill, S.C., USA) to yield a composite. Thecomposite was placed on the High Gloss tool such that the EMAA filmcontacted the aluminum reflective layer. The entire construction wassandwiched between several layers of flat aluminum plates and 0.0024inch (0.061 mm) polyester film. Using a Hix Model N-800 press (availablefrom Hix Corporation, Pittsburg, Kans., USA) set to a temperature ofabout 250° F. (121° C.), a pressure of about 40 psi (275 kPa), and adwell time of about 10 minutes, the composite was laminated to the HighGloss tool. After cooling, the High Gloss tool was separated from themolding polymer to yield a retroreflective article. The separationcaused the reflective layer to transfer from the High Gloss tool to themolding polymer. The article had cube-corner shaped cavities with analuminum reflective layer coated on the optical faces. The article had abrightness measurement of about 577 candelas/lux/meter².

Example 2

[0086] A retroreflective article was made according to Example 1 exceptthat the molding polymer was a 0.002 inch (0.051 mm) linear co-polyesterfilm (available as product number “5250” from Bemis Associates, Shirley,Mass., USA). The molding polymer was laminated to the aluminum coatedHigh Gloss tool using the Hix press under substantially the sameprocessing conditions as in Example 1. After the entire construction wascooled, a 100% polyester fabric (available from Milliken Co.,Spartanburg, S.C., USA) was laminated to the flat, i.e., non-structured,side of the molding polymer. The resulting retroreflective article hadplurality of cube-corner shaped cavities formed from the co-polyesterfilm molding polymer, an aluminum reflective layer coated on the opticalfaces of the cavities, and a polyester fabric carrier supporting themolding polymer. The article had a brightness measurement of about 691candelas/lux/meter².

Example 3

[0087] A retroreflective article was made according to Example 1 exceptthat the molding polymer was a 0.010 inch thick (0.254 mm)semi-crystalline polyamide film. The film was made by extrudingVestamelt 450-P2 resin powder (available from Creanova Inc., Sommerset,N.J., USA) onto a 0.0024 inch (0.061 mm) polyester liner using standardextrusion coating methods. The molding polymer was laminated to thepreviously aluminum coated High Gloss tool using the Hix press undersubstantially the same processing conditions as in Example 1.

[0088] After the entire construction was cooled, the polyester liner wasstripped off and a 100% polyester fabric (available from Milliken Co.,Spartanburg, S.C., USA) was laminated to the flat, i.e., non-structured,side of the molding polymer. The resulting retroreflective article hadplurality of cube-corner shaped cavities formed from the polyamide filmmolding polymer, an aluminum reflective layer coated on the opticalfaces of the cavities, and a polyester fabric carrier supporting themolding polymer. The article had a brightness measurement of about 622candelas/lux/meter².

Example 4

[0089] A retroreflective article was made according to Example 1 exceptthat the molding polymer was a 0.002 inch thick (0.051 mm) high meltingpolyester film. The film was made by extruding Dynapol S1359 resin(available from Creanova Inc., Sommerset, N.J., USA) onto a 0.0024 inch(0.061 mm) polyester liner using standard extrusion coating methods. Themolding polymer was laminated to the aluminum coated High Gloss toolusing the Hix press under substantially the same processing conditionsas in Example 1.

[0090] After the entire construction was cooled, the polyester liner wasstripped off and a 100% polyester fabric (available from Milliken Co.,Spartanburg, S.C., USA) was laminated to the flat, i.e., non-structured,side of the molding polymer. The resulting retroreflective article hadplurality of cube-corner shaped cavities formed from the high meltingpolyester film molding polymer, an aluminum reflective layer coated onthe optical faces of the cavities, and a polyester fabric carriersupporting the molding polymer. The article had a brightness measurementof about 512 candelas/lux/meter².

Example 5

[0091] A retroreflective article was made according to Example 1 exceptthat the molding polymer was a 0.002 inch thick (0.051 mm) polyurethanefilm (available as product number “3218” from Bemis Associates, Shirley,Mass., USA). The molding polymer was laminated to the aluminum coatedHigh Gloss tool using the Hix press under substantially the sameprocessing conditions as in Example 1.

[0092] After the entire construction was cooled, a 100% polyester fabric(available from Milliken Co., Spartanburg, S.C., USA) was laminated tothe flat, i.e., nonstructured, side of the molding polymer. Theresulting retroreflective article had plurality of cube-corner shapedcavities formed form the polyurethane film molding polymer, an aluminumreflective layer coated on the optical faces of the cavities, and apolyester fabric carrier supporting the molding polymer. The article hada brightness measurement of about 48 candelas/lux/meter².

Example 6

[0093] A sample was made to determine the adhesion (using a 90° peeltest) between an acrylate molding polymer film and an aluminumreflective layer. The sample was made as follows. On a clear, colorlessPET based liner having a thickness of about 0.002 to 0.004 inch (0.05 to0.10 mm), an acrylate solution was coated using conventional coatingtechniques, such as notch bar coating, to a dry thickness of about0.0002 to 0.0005 inch (0.005-0.013 mm). The resin solution was made fromthe following formulation: 1,6 hexanediol diacrylate, trimethylolpropanetriacrylate, and bisphenol A epoxy diacrylate, in a ratio of 25:50:25parts by weight with 1% resin weight Darocurr™ 4265 as photoinitator(available from Ciba Geigy Corporation). The resin solution was curedthrough the PET liner with a FUSION H lamp (available from Fusion UVCuring Systems, Gaithersburg, Md., USA) operating at about 235 watt/cmat a line speed of 25 ft/min (7.6 m/min), and then postcured from theacrylate side with the FUSION H lamp at substantially similar processingconditions, as stated above. The resulting intermediate sample is a PETbased liner having an acrylate molding polymer disposed on it, theacrylate layer molding polymer having a first side in direct contactwith the PET based liner and a second side that is exposed.

[0094] On the exposed side of the acrylate, an aluminum reflective layerwas deposited using an electron beam vacuum coater pulling a vacuum ofabout 6×10⁻⁶ torr and an evaporation rate of about 18 to 24 angstromsper second. The aluminum reflective layer was about 800 to 1000 nmthick. The resulting sample is an aluminum coated acrylate compositedisposed on a PET based liner.

[0095] The adhesion between the aluminum reflective layer and theacrylate molding polymer was tested. The acrylate composite made abovewas cut to 1 inch by 6 inch (2.54 cm by 15.2 cm) sample and thenattached to a T-6061 aluminum panel that was previously heat laminatedwith an ethylene acrylic acid (EAA) adhesive layer that was about 2 inchby 6 inch (5.08 by 15.2 cm). The EAA layer was about 0.002 to 0.003 inchthick (0.05 to 0.08 mm). The sample was not completely attached to theEAA but instead, one end of the sample, about 1 inch long, waspurposefully left unattached. The sample was attached such that thealuminum reflective layer was in direct contact with the EAA. Theattached sample was conditioned at ambient conditions (generally about70° F.) for about 24 hours before testing.

[0096] After conditioning, the attached sample was placed in a tensiletesting machine known under the trade designation SINTECH (availablefrom SINTECH, a division of MTS Systems, Eden Prairie, Minn., USA) andsubjected to the 90° Peel Back test as follows. The entire construction(test panel and sample) was slipped into a test holder such that thepanel was held down on several of the edges, but sample was exposed andlied parallel to the bottom of the SINTECH-1 unit. The unattached end ofthe sample was bent at 90° and clamped to the upper test grip of theSINTECH-1. The sample was pulled back in such a fashion it made a 90°angle with the test panel. The sample was pulled back at a constant headspeed of about 12 inches/min (30 cm/min). Because the adhesion betweenthe aluminum reflective layer and the EAA is much greater than theadhesion between the aluminum reflective layer and the acrylate moldingpolymer, the failure occurred between the aluminum and the acrylate.That is to say, as the sample is being pulled back, the aluminum stayedwith the EAA. The peel strength was measured to be about 0.2 pounds perinch width, representing the adhesion value between the aluminum and theacrylate.

[0097] All references cited above, including patents discussed in theBackground, are incorporated by reference in their entirety into thisdocument.

[0098] The present invention may be suitably practiced in the absence ofany element or item not specifically described in this document.

What is claimed is:
 1. A method of making a retroreflective article,which method comprises: (a) providing a device comprising a firststructured surface; (b) applying a reflective layer on the firststructured surface such that a first adhesion value is establishedbetween the reflective layer and the first structured surface, thereflective layer having an exposed surface; (c) applying a moldingpolymer to the exposed surface of the reflective layer such that asecond adhesion value is established between the reflective layer andthe molding polymer, the second adhesion value being higher than thefirst adhesion value; and (d) separating the device from the moldingpolymer to yield the retroreflective article having a second structuredsurface, the separation causing a transfer of the reflective layer fromthe first structured surface to the retroreflective article.
 2. Themethod of claim 1 wherein the device is a tool having a plurality ofcube-corner elements defining the first structured surface.
 3. Themethod of claim 1 , wherein after step (c), the method further comprisesthe steps of: (a) contacting a carrier web to the molding polymer; (b)minimizing excess molding polymer extending above the first structuredsurface; and then (c) curing the molding polymer while in contact withthe carrier web.
 4. The method of claim 3 , wherein the device is a moldhaving a plurality of cube-corner shaped cavities defining the firststructured surface.
 5. The method of claim 1 , wherein the reflectivelayer is adhesively attached to the second structured surface.
 6. Themethod of claim 1 , wherein the reflective layer is selected from thegroup consisting of aluminum, silver, tin, and gold.
 7. The method ofclaim 1 , wherein after step (d), the method further comprises applyinga light transmissible protective layer on the reflective layer disposedon the second structured surface of the retroreflective article.
 8. Themethod of claim 7 , wherein the protective layer further comprises alight transmissible colorant.
 9. The method of claim 7 , wherein saidprotective layer is selected from a group consisting of lighttransmissible mercaptan, organosilicone, acrylic, and polyurethane. 10.The method of claim 1 , wherein after step (b), the method furthercomprises applying a tie layer on the exposed surface of the reflectivelayer.
 11. The method of claim 1 wherein the molding polymer is selectedfrom the group consisting of extrudable resin, actinic curable resin,and reaction curable resin.
 12. The method of claim 1 , wherein themolding polymer is a thermoplastic polymer selected from the groupconsisting of ethylene copolymers containing carboxyl groups or estersof carboxylic acids, polyethylene acrylate, polyesters, linearcopolyesters, polyurethanes, polyester amides, polyamides, andcrystalline rubber based polymers.
 13. The method of claim 1 , whereinthe molding polymer is thermoplastic polymer having a softeningtemperature less than about 450° F. as determined by ASTM E 28-97. 14.The method of claim 1 , wherein the molding polymer is applied to thereflective layer using a method selected from the group consisting oflaminating, extruding, screen printing, and coating.
 15. The method ofclaim 1 further comprising supporting the molding polymer with a carrierselected from the group consisting of fabric and polymer film.
 16. Themethod of claim 1 , wherein the first structured surface is a polymerselected from the group consisting of polycarbonate and acrylate. 17.The method of claim 16 , wherein the reflective layer is aluminum.
 18. Amethod of making a retroreflective article, which method comprises: (a)providing a device comprising a first structured surface; (b) applying aprotective layer on the first structured surface such that a firstadhesion value is established between the protective layer and the firststructured surface, the protective layer having an exposed surface; (c)applying a reflective layer on the exposed surface of the protectivelayer such that a second adhesion value is established between theprotective layer and the reflective layer; (d) applying a moldingpolymer to the exposed surface of the reflective layer such that a thirdadhesion value is established between the reflective layer and themolding polymer, the second and third adhesion values being higher thanthe first adhesion value; and (e) separating the device from the moldingpolymer to yield the retroreflective article having a second structuredsurface, the separation causing a transfer of the protective andreflective layers from the first structured surface to theretroreflective article.
 19. The method of claim 18 , wherein theprotective layer further comprises a light transmissible colorant.
 20. Aretroreflective article that comprises: (a) a structured surface that isconfigured for allowing the article to retroreflect incident light; and(b) an aluminum reflective layer disposed on the structured surface, thealuminum layer having first and second sides, the first side disposedtowards the structured surface and lies opposite the second side,wherein the first side has an aluminum microstructure is in apredominantly amorphous arrangement, and wherein the second side has analuminum microstructure in a predominantly crystalline arrangement. 21.The retroreflective article of claim 20 , wherein the structured surfacecomprises a plurality of cube-corner structures selected from the groupconsisting of cube-corner elements, cube-corner shaped cavities andcombinations thereof.
 22. The retroreflective article of claim 20 ,wherein the cube-corner structures are bound by three optical facescooperating to retroreflect incident light.
 23. The retroreflectivearticle of claim 22 , wherein the cube-corner structures furthercomprise a non-optical face.
 24. The retroreflective article of claim 20, further comprising a light transmissible protective layer disposed onthe reflective layer.
 25. The retroreflective article of claim 24 ,wherein the protective layer further comprises a light transmissiblecolorant.
 26. The retroreflective article of claim 24 , wherein theprotective layer substantially covers the structured surface.
 27. Theretroreflective article of claim 24 , wherein the protective layerfollows the topography of the structured surface.
 28. Theretroreflective article of claim 20 , wherein the structured surface isformed from a molding polymer.
 29. The retroreflective article of claim28 , wherein the molding polymer is a thermoplastic polymer selectedfrom the group consisting of ethylene copolymers containing carboxylgroups or esters of carboxylic acids, polyethylene acrylate, polyesters,linear co-polyesters, polyurethanes, polyester amides, polyamides, andcrystalline rubber based polymers.
 30. The retroreflective article ofclaim 28 , wherein the molding polymer is an adhesive selected from thegroup consisting of hot melt adhesive, pressure sensitive adhesive, andscreen printable adhesive.
 31. The retroreflective article of claim 28 ,wherein the molding polymer has a softening temperature of less thanabout 450° F. as determined by ASTM E 28-97.
 32. The retroreflectivearticle of claim 28 , wherein the molding polymer is a thermoset. 33.The retroreflective article of claim 20 , wherein the aluminumreflective layer is attached adhesively to the structured surface.